TWI709480B - Interlayer film for laminated glass and laminated glass - Google Patents

Abstract

The object of the present invention is to provide an interlayer film for laminated glass that can be produced in a vacuum degassing method that can exhibit high degassing and high transparency laminated glass, and a layer using the interlayer film for laminated glass He glass.

The interlayer film for laminated glass of the present invention has a plurality of recesses on at least one surface, and the recesses have a groove shape with a continuous bottom, and the adjacent recesses of the continuous bottom groove are arranged regularly, and the grooves with continuous bottom The radius of rotation R at the bottom of the recess is 45 μm or less.

Description

Interlayer film for laminated glass and laminated glass

The present invention relates to an interlayer film for laminated glass that can be produced in a vacuum degassing method that can exhibit high degassing and high transparency of laminated glass, and a laminated glass using the interlayer film for laminated glass glass.

The laminated glass formed by sandwiching an interlayer film for laminated glass containing thermoplastic resins such as plasticized polyvinyl butyral and so on between two glass plates is widely used as windshield for automobiles.

As one of the manufacturing methods of such automobile windshield, vacuum degassing method can be performed.

In the vacuum degassing method, the laminated body with the interlayer film for laminated glass laminated between at least two glass plates is put into a rubber bag for reduced pressure suction, while leaving the residue between the glass plate and the interlayer film The air is removed while pre-compression bonding is performed, and then, for example, it is heated and pressurized in an autoclave to perform full-compression bonding, thereby obtaining a windshield for automobiles.

In the manufacturing process of laminated glass by the vacuum degassing method, what is important is the degassing property of the laminated glass and the interlayer film for laminated glass. Therefore, in order to ensure the degassing performance when manufacturing laminated glass, fine unevenness is formed on at least one surface of the interlayer film for laminated glass. especially By forming the concave portion in the concavity and convexity into a groove shape having a continuous bottom, and the adjacent concave portions of the groove shape are formed in parallel and regularly, extremely excellent degassing properties can be exerted (for example, Patent Document 1).

However, even if such an interlayer film for laminated glass having continuous groove-shaped recesses on the surface is used to manufacture laminated glass by the vacuum degassing method, there is a problem that the outgassing becomes insufficient and remains in the interlayer film The air causes foaming, and the transparency of the laminated glass may decrease.

[Prior Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2001-48599

The object of the present invention is to provide an interlayer film for laminated glass that can be produced in a vacuum degassing method that can exhibit high degassing and high transparency laminated glass, and a layer using the interlayer film for laminated glass He glass. Furthermore, the interlayer film for laminated glass of the present invention can also be used other than the vacuum degassing method.

The interlayer film for laminated glass of the present invention has a plurality of recesses on at least one surface, and the recesses have a groove shape with a continuous bottom, and the adjacent recesses of the continuous bottom groove are arranged regularly, and the grooves with continuous bottom The radius of rotation R at the bottom of the recess is 45 μm or less.

Hereinafter, the present invention will be described in detail.

The inventors of the present invention studied the reasons why the transparency of the laminated glass obtained when the laminated glass is manufactured by the vacuum degassing method is reduced.

In the vacuum degassing method, in the pre-compression bonding, the laminated body with the interlayer film for laminated glass laminated between at least two glass plates is put into a rubber bag for vacuum suction, and the remaining on the glass plate and After the air between the interlayer films is removed, the interlayer film for laminated glass at the end of the laminate is brought into close contact with the glass by heating to seal. With this kind of sealing, the inside can be kept in a vacuum state even after being taken out from the rubber bag, and air intrusion can be prevented until the formal crimping. In actual production, in order to shorten the manufacturing time, degassing and heating are performed at the same time.

The inventors of the present invention conducted diligent studies and found that when degassing and heating are performed simultaneously during the pre-compression bonding, before the degassing is fully completed, the interlayer film for the laminated glass and the glass are sealed at the end of the laminate, resulting in insufficient Degassing is performed, and a large amount of air remains inside the laminate (hereinafter also referred to as "pre-sealing"). After the pre-sealed laminate is heated and pressurized in the autoclave during the formal crimping, the remaining air causes foaming, which causes the transparency of the laminated glass to decrease.

In order to prevent pre-sealing, consider increasing the roughness of the continuous groove at the bottom so that the groove is not easily disintegrated and extending the time until it is sealed. However, when the roughness is increased, the bottom is crimped The continuous groove is not fully disintegrated, but degassing becomes insufficient.

The inventors of the present invention conducted further studies and found that by setting the radius of rotation R of the bottom of the groove-shaped concave portion with a continuous bottom to 45μm or less, it can be manufactured in a vacuum degassing method with high degassing and transparency. Laminated glass with higher performance, thus completing the present invention.

Furthermore, the interlayer film for laminated glass of the present invention can also be used other than the vacuum degassing method.

The interlayer film for laminated glass of the present invention has a plurality of recesses on at least one surface. The recesses have a groove shape with a continuous bottom, and the adjacent recesses of the groove shape with a continuous bottom are arranged regularly. Thereby, it is possible to ensure the deaeration performance when manufacturing laminated glass by the vacuum deaeration method. The above-mentioned recesses may be formed on only one surface, and in terms of significantly improving the degassing properties, they are preferably formed on laminated glass Use both sides of the intermediate film.

In the interlayer film for laminated glass of the present invention, the recesses on the at least one surface have a groove shape with a continuous bottom (that is, a "line-shaped recess"), and adjacent recesses are regularly aligned. Generally, when a laminated body formed by laminating an intermediate film for laminated glass between two glass plates is crimped, the ease of air removal is closely related to the connectivity and smoothness of the bottom of the recess. By making the recesses on at least one surface of the intermediate film into a shape in which the recesses in the form of engraved lines are arranged regularly, the connectivity of the bottom is more excellent, and the outgassing property is significantly improved. In addition, the recesses on the scribed lines need not be groove-shaped with all the bottoms continuous, and a partition wall may be provided at a part of the bottom. In addition, as long as the adjacent recesses are arranged in parallel and regularly, the shape of the groove at the bottom does not need to be linear, for example, it may have a wave shape or a zigzag shape.

Fig. 1 and Fig. 2 show schematic diagrams showing an example of an interlayer film for laminated glass in which engraved recesses are arranged in parallel at equal intervals.

Fig. 3 shows a schematic diagram showing an example of an interlayer film for laminated glass in which engraved recesses are arranged in parallel at different intervals. In FIG. 3, the interval A between the concave portion 1 and the concave portion 2 is different from the interval B between the concave portion 1 and the concave portion 3.

In the interlayer film for laminated glass of the present invention, the rotation radius R of the bottom of the groove-shaped concave portion having the continuous bottom is 45 μm or less. As a result, it is possible to prevent pre-sealing, and it is possible to manufacture laminated glass that can exhibit high degassing properties and high transparency in the vacuum degassing method. It is believed that the reason is that by making the radius of rotation R of the bottom of the concave portion of the continuous groove at the bottom smaller than the conventional interlayer film for laminated glass, even if the roughness of the continuous groove of the bottom is not increased, the When degassing and heating are performed at the same time during connection, the sealing of the interlayer film for laminated glass at the end of the laminate and the glass can be delayed until the degassing is fully completed. The rotation of the bottom of the continuous groove-shaped concave part The radius of rotation R is preferably 40 μm or less, more preferably 30 μm or less, still more preferably 15 μm or less, and particularly preferably 10 μm or less. On the other hand, the lower limit of the radius of rotation R of the bottom of the continuous groove-shaped concave portion is not particularly limited, and is substantially 0.001 μm. The radius of rotation R of the bottom of the concave portion with the continuous groove-shaped bottom is preferably 0.1 μm or more, more preferably 1 μm or more. By setting the radius of rotation R of the bottom to be greater than the above value, it is possible to prevent the recess from being sealed in a state where the recess is not disintegrated at all during the pre-compression bonding.

Furthermore, when the interlayer film for laminated glass of the present invention has a plurality of concave portions on both sides, and the concave portion has a groove shape with a continuous bottom, and the adjacent concave portions of the continuous bottom groove are arranged regularly, any one The radius of rotation R of the bottom of the continuous groove-shaped recess in the surface should be 45 μm or less.

The interlayer film for laminated glass of the present invention preferably has a plurality of recesses on one surface and a surface opposite to the one surface, and the recesses have a groove shape with a continuous bottom. The presence of the above-mentioned recesses on both sides significantly improves the outgassing performance.

In addition, when vacuum suction is performed in the pre-compression bonding, in order to disperse the direction of the exhaust gas and smoothly degas, it is preferable that the concave portion of the bottom continuous groove on the one surface and the opposite side The intersection angle θ of the groove-shaped recesses with the continuous bottom on the surface exceeds 0°, more preferably 20° or more, and most preferably 90°. Furthermore, the above-mentioned intersection angle θ refers to the acute angle formed by the concave portion of the groove-shaped bottom continuous on the one surface and the concave portion of the groove-shaped bottom continuous groove on the opposite surface.

In this manual, the radius of rotation R of the bottom of the groove-shaped recess with the continuous bottom can be obtained by the following method: using a single-edged razor (for example, manufactured by FEATHER Safety Razor, FAS-10), along the line continuous with the bottom The direction of the groove-shaped recess is perpendicular, and Parallel to the film thickness direction to avoid deformation of the cut surface, press the razor in a direction parallel to the thickness direction without sliding in the direction perpendicular to the recess, thereby cutting the interlayer film for laminated glass , Use a microscope (for example, "DSX-100" manufactured by Olympus) to observe the cross-section, and take a picture with a measuring magnification of 277 times, and then use the attached image with a magnification of 50μm/20mm. The measurement software in the software sets the radius of the circle inscribed to the bottom of the groove-shaped recess that is continuous with the bottom as the radius of rotation R of the recess. In addition, the environment at the time of measurement was 23°C and 30RH%. Here, take any 5 points in the interlayer film for laminated glass, measure 3 points for each sample, and use the average value of 15 points as R.

Fig. 4 shows a schematic diagram illustrating the radius of rotation R of the bottom of the concave portion with a continuous groove at the bottom and the interval Sm of the concave portion. In Fig. 4(a), the surface 20 of the interlayer film for laminated glass has a groove-shaped recess 21 with a continuous bottom. Sm means the interval between the recesses 21. In addition, in FIG. 4(b), when a circle is drawn in a form in contact with the bottom of the recess 21, the radius of the circle is R.

In the interlayer film for laminated glass of the present invention, when the roughness curve is drawn in accordance with JIS B 0601 (1994) in the direction of the line connecting the shortest distance between the bottom of the continuous groove-shaped recesses at the bottom of adjacent It is preferable that the point where the height reaches the maximum is not at the center of the line of the shortest distance between the bottom of the connection.

Figure 5 shows the direction of the line along the shortest distance between the bottoms of continuous groove-shaped recesses that connect adjacent bottoms. When the roughness curve is drawn according to JIS B 0601 (1994), the point where the height reaches the maximum is not located at the bottom of the connection. A schematic diagram of the interlayer film for laminated glass at the center of the line of the shortest distance between the bottoms. According to Figure 5, the phrase "the point of maximum height is not located at the center of the line connecting the shortest distance between the bottoms" means the shortest distance between the bottoms of the continuous groove-shaped recesses connecting the adjacent bottoms. Draw the shortest distance perpendicular to the bottom of the above link The shape of the concave portion of the continuous groove at the bottom of the adjacent line is asymmetrical when the vertical line is the axis. Therefore, by making the shape of the groove-shaped concave portion of the adjacent bottom continuous groove asymmetrical, the radius of rotation R of the bottom of the groove-shaped concave portion of the continuous bottom groove can easily be 45 μm or less.

In the interlayer film for laminated glass of the present invention, it is preferable that the interval Sm between the groove-shaped recesses having the continuous bottom is 400 μm or less. As a result, when the laminated glass is manufactured by the vacuum degassing method, it is easier to exhibit better degassing performance during pre-compression bonding, and it is easier to disintegrate the continuous groove-shaped recesses at the bottom by the pressure . The interval Sm of the groove-shaped recesses having the continuous bottom is more preferably 300 μm or less.

The lower limit of the interval Sm between the continuous groove-shaped recesses at the bottom is preferably 100 μm, and more preferably, the lower limit is 150 μm.

Furthermore, the interval Sm of the groove-shaped recesses with the continuous bottom in this specification is specified by JIS B 0601 (1994). Regarding the measurement conditions, for example, the measurement can be performed under the conditions of reference length = 2.5 mm, evaluation length 12.5 mm, stylus tip radius = 2 μm, tip angle = 60°, and measurement speed = 0.5 mm/s. Here, the arbitrary 5 points in the interlayer film for laminated glass are measured, and the average value is made into Sm.

In the interlayer film for laminated glass of the present invention, it is preferable that the roughness Rz of the groove-shaped concave portion with a continuous bottom is 60 μm or less. As a result, when the laminated glass is manufactured by the vacuum degassing method, it is easier to exhibit better degassing performance during pre-compression bonding, and it is easier to disintegrate the continuous groove-shaped recesses at the bottom by the pressure . The roughness Rz of the groove-shaped concave portion having the continuous bottom is more preferably 50 μm or less.

The lower limit of the roughness Rz of the concave portion of the continuous groove shape at the bottom is preferably 10μm, more preferably The lower limit is 20μm.

In addition, the roughness Rz of the concave portion of the continuous groove at the bottom in this specification is specified by JIS B 0601 (1994).

In the interlayer film for laminated glass of the present invention, it is preferable that the above-mentioned surface with a plurality of concave portions further has a plurality of convex portions, and the top of the convex portion is not flat. As a result, during pre-compression bonding, more excellent degassing properties can be exerted.

The interlayer film for laminated glass of the present invention may have a single-layer structure composed of only one resin film, or a multilayer structure in which two or more resin layers are laminated.

When the interlayer film for laminated glass of the present invention has a multi-layer structure, by having the first resin layer and the second resin layer as two or more resin layers, and the first resin layer and the second resin layer have different Properties, it can provide an interlayer film for laminated glass with various properties that are difficult to achieve with only one layer.

The resin layer preferably contains a thermoplastic resin.

Examples of the above-mentioned thermoplastic resins include: polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-hexafluoropropylene copolymer, polytrifluoroethylene, acrylonitrile-butadiene-styrene copolymer, polyester , Polyether, polyamide, polycarbonate, polyacrylate, polymethacrylate, polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyvinyl acetal, ethylene-vinyl acetate copolymer, etc. Among them, the thermoplastic resin preferably contains polyvinyl acetal or an ethylene-vinyl acetate copolymer, and more preferably contains polyvinyl acetal.

The above-mentioned polyvinyl acetal can be produced, for example, by acetalizing polyvinyl alcohol (PVA) with aldehyde. The polyvinyl acetal is preferably an acetal product of polyvinyl alcohol. The saponification degree of PVA is usually in the range of 70~99.9 mol%.

The degree of polymerization of the PVA used to obtain the polyvinyl acetal is preferably 200 or more, more preferably 500 or more, more preferably 1700 or more, particularly preferably 2000 or more, and preferably 5000 or less, more preferably 4000 or less , More preferably 3000 or less, still more preferably less than 3000, and particularly preferably 2800 or less. The polyvinyl acetal is preferably a polyvinyl acetal obtained by acetalizing PVA having a degree of polymerization of not less than the above lower limit and not more than the above upper limit. If the degree of polymerization is greater than or equal to the lower limit, the penetration resistance of the laminated glass becomes higher. If the degree of polymerization is equal to or less than the upper limit, the formation of the interlayer film becomes easy.

The degree of polymerization of PVA means the average degree of polymerization. The average degree of polymerization can be determined by a method based on JIS K6726 "Test Method for Polyvinyl Alcohol". As the above-mentioned aldehydes, aldehydes having 1 to 10 carbon atoms are usually preferably used. Examples of aldehydes having 1 to 10 carbon atoms include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexanal, n-octanal, and Nonanal, n-decanal and benzaldehyde, etc. Among them, n-butyraldehyde, n-hexanal or n-valeraldehyde is preferred, and n-butyraldehyde is more preferred. Only one kind of the above-mentioned aldehyde may be used, or two or more kinds may be used in combination.

The above-mentioned polyvinyl acetal is preferably polyvinyl butyraldehyde. By using polyvinyl butyral, the weather resistance of the interlayer film for laminated glass and the laminated glass is further improved.

The resin layer preferably contains polyvinyl acetal and a plasticizer.

The above-mentioned plasticizer is not particularly limited as long as it is a plasticizer commonly used for interlayer films for laminated glass, and examples thereof include organic plasticizers such as monobasic organic acid esters and polybasic organic acid esters; or organic phosphoric acid compounds , Organic phosphorous compounds and other phosphoric acid plasticizers, etc.

As the above-mentioned organic plasticizer, for example, triethylene glycol bis(2-ethylhexanoate), triethylene glycol bis(2-ethylbutyrate), triethylene glycol bis(n-heptanoic acid) Ester), tetraethylene glycol bis (2-ethylhexanoate), tetraethylene glycol bis (2-ethyl butyrate), tetraethylene glycol bis (n-heptanoate), Diethylene glycol bis(2-ethylhexanoate), diethylene glycol bis(2-ethylbutyrate), diethylene glycol bis(n-heptanoate) and the like. Among them, the above-mentioned organic plasticizer preferably contains triethylene glycol bis (2-ethylhexanoate), triethylene glycol bis (2-ethyl butyrate), or triethylene glycol bis (n-heptyl Ester), more preferably contains triethylene glycol bis(2-ethylhexanoate).

It is preferable that the said resin layer contains an adhesive force regulator. In particular, when manufacturing laminated glass, the resin layer in contact with the glass preferably contains the above-mentioned adhesive strength regulator.

As the adhesive strength regulator, for example, an alkali metal salt or an alkaline earth metal salt can be preferably used. Examples of the aforementioned adhesive strength modifier include salts of potassium, sodium, and magnesium.

Examples of the acid constituting the salt include organic acids such as caprylic acid, caproic acid, 2-ethylbutyric acid, butyric acid, acetic acid, and formic acid; or inorganic acids such as hydrochloric acid and nitric acid. When manufacturing a laminated glass, in terms of easily adjusting the adhesive force between the glass and the resin layer, the resin layer in contact with the glass preferably contains a magnesium salt as an adhesive force modifier.

The above-mentioned resin layer may optionally contain additives such as antioxidants, light stabilizers, modified silicone oils as adhesive modifiers, flame retardants, antistatic agents, moisture resistant agents, heat reflecting agents, and heat absorbing agents.

The interlayer film for laminated glass of the present invention preferably contains at least one metal selected from the group consisting of alkali metals, alkaline earth metals, and magnesium. By containing at least one metal selected from the group consisting of alkali metals, alkaline earth metals, and magnesium, the adhesive force of the interlayer film for laminated glass to the glass can be adjusted, and a laminate with higher penetration resistance can be obtained glass.

From the viewpoint of further improving the penetration resistance of the laminated glass, the lower limit of the content of at least one metal selected from the group consisting of alkali metals, alkaline earth metals and magnesium is preferably 1 ppm, and more preferably 5 ppm, and further The lower limit is preferably 20ppm, and the lower limit is more preferably 50 ppm. Regarding the prevention of peeling by adjusting the adhesive force between the interlayer film for laminated glass and the glass, it is possible to further prevent poor sealing at the time of pre-compression bonding, the above is selected from the group consisting of alkali metals, alkaline earth metals and magnesium A preferable upper limit of the content of at least one metal is 500 ppm, a more preferable upper limit is 300 ppm, a further preferable upper limit is 150 ppm, and a particularly preferable upper limit is 100 ppm.

In the interlayer film for laminated glass of the present invention, it is preferable to have at least a first resin layer and a second resin layer as two or more resin layers, and the polyvinyl acetal contained in the first resin layer (hereinafter referred to as The amount of hydroxyl groups in polyvinyl acetal A) is different from the amount of hydroxyl groups in polyvinyl acetal (hereinafter referred to as polyvinyl acetal B) contained in the second resin layer.

Since the properties of polyvinyl acetal A and polyvinyl acetal B are different, it is possible to provide an interlayer film for laminated glass with various properties that are difficult to achieve with only one layer. For example, when the first resin layer is laminated between the two second resin layers, and the amount of hydroxyl groups of polyvinyl acetal A is lower than the amount of hydroxyl groups of polyvinyl acetal B, the first resin layer The glass transition temperature tends to be lower than that of the second resin layer. As a result, the first resin layer becomes softer than the second resin layer, and the sound insulation of the interlayer film for laminated glass becomes higher. Furthermore, when the first resin layer is laminated between the two second resin layers, and the amount of hydroxyl groups of polyvinyl acetal A is higher than the amount of hydroxyl groups of polyvinyl acetal B, the first resin layer The glass transition temperature tends to be higher than that of the second resin layer. As a result, the first resin layer becomes harder than the second resin layer, and the penetration resistance of the interlayer film for laminated glass becomes higher.

Furthermore, when the first resin layer and the second resin layer contain a plasticizer, the content of the plasticizer in the first resin layer relative to 100 parts by mass of polyvinyl acetal (hereinafter referred to as The content A) is different from the content of the plasticizer in the second resin layer with respect to 100 parts by mass of polyvinyl acetal (hereinafter referred to as content B). For example, in the above second tree on two levels When the first resin layer is laminated between the grease layers, and the content A is more than the content B, the first resin layer tends to have a lower glass transition temperature than the second resin layer. As a result, the first resin layer becomes softer than the second resin layer, and the sound insulation of the interlayer film for laminated glass becomes higher. In addition, when the first resin layer is laminated between the two second resin layers, and the content A is less than the content B, the first resin layer has glass compared to the second resin layer. The tendency of the transition temperature to become higher. As a result, the first resin layer becomes harder than the second resin layer, and the penetration resistance of the interlayer film for laminated glass becomes higher.

When the interlayer film for laminated glass of the present invention has a laminate structure of three or more layers, it preferably has a laminate structure having a first resin layer, a second resin layer, and a third resin layer in this order along the thickness direction. Furthermore, for example, from the viewpoint of imparting various functions such as high impact resistance to the interlayer film for laminated glass, it is preferable that the thickness of the first resin layer and the thickness of the third resin layer are different. The thickness of the first resin layer and the thickness of the third resin layer are preferably different by 10 μm or more, more preferably by 50 μm or more, and still more preferably by 100 μm or more. The upper limit of the difference between the thickness of the first resin layer and the thickness of the third resin layer is not particularly limited, but is substantially 1000 μm or less.

As a combination of two or more resin layers constituting the interlayer film for laminated glass of the present invention, for example, in order to improve the sound insulation of laminated glass, the sound insulation layer as the first resin layer and the second resin Combination of protective layers of layers. In terms of improving the sound insulation of the laminated glass, it is preferable that the sound insulation layer contains polyvinyl acetal X and a plasticizer, and the protective layer contains polyvinyl acetal Y and a plasticizer. Furthermore, when the sound insulation layer is laminated between the two protective layers, an interlayer film for laminated glass having excellent sound insulation properties (hereinafter also referred to as a sound insulation interlayer film) can be obtained. For example, to make the interlayer film for laminated glass exert high impact resistance From the viewpoint of imparting various functions such as sex, in the case of having two or more protective layers, it is preferable that the thickness of each protective layer is different. Hereinafter, the sound insulation interlayer film will be described in more detail.

In the above sound insulation interlayer film, the sound insulation layer has a function of imparting sound insulation. The sound-insulating layer preferably contains polyvinyl acetal X and a plasticizer.

The above-mentioned polyvinyl acetal X can be prepared by acetalizing polyvinyl alcohol with aldehyde. The above-mentioned polyvinyl alcohol is usually obtained by saponifying polyvinyl acetate.

The preferred lower limit of the average degree of polymerization of the polyvinyl alcohol is 200, and the preferred upper limit is 5,000. By setting the average degree of polymerization of the polyvinyl alcohol to 200 or more, the penetration resistance of the obtained sound insulation interlayer film can be improved, and by setting it to 5000 or less, the formability of the sound insulation layer can be ensured. The lower limit of the average degree of polymerization of the polyvinyl alcohol is more preferably 500, and the upper limit is more preferably 4,000.

In addition, the average degree of polymerization of the above-mentioned polyvinyl alcohol can be obtained by a method based on JIS K6726 "Testing Methods for Polyvinyl Alcohol".

The preferable lower limit of the carbon number of the aldehyde used to acetalize the polyvinyl alcohol is 4, and the preferable upper limit is 6. By setting the carbon number of the aldehyde to 4 or more, a sufficient amount of plasticizer can be stably contained, and excellent sound insulation performance can be exerted. In addition, it can prevent the exudation of the plasticizer. By setting the carbon number of the aldehyde to 6 or less, the synthesis of polyvinyl acetal X can be facilitated and productivity can be ensured. The aldehyde having 4 to 6 carbon atoms may be linear or branched. For example, n-butyraldehyde, n-valeraldehyde, etc. may be mentioned.

The preferable upper limit of the hydroxyl group content of the polyvinyl acetal X is 30 mol%. By setting the amount of the hydroxyl group of the polyvinyl acetal X to be 30 mol% or less, the plasticizer can be contained in an amount required for the sound insulation, and the oozing of the plasticizer can be prevented. The more preferable upper limit of the hydroxyl group content of the polyvinyl acetal X is 28 mol%, and the more preferable upper limit is 26 mol%, and the more preferable upper limit is 24 The lower limit is preferably 10 mol%, and the lower limit is more preferably 15 mol%, and the lower limit is more preferably 20 mol%. The amount of hydroxyl groups in the polyvinyl acetal X is a value expressed as a percentage (mole%) obtained by dividing the amount of ethylene groups bound by the hydroxyl group by the total amount of ethylene groups in the main chain. The amount of ethylene groups to which the hydroxyl group is bonded can be determined by, for example, measuring the amount of ethylene groups to which the hydroxyl group of the polyvinyl acetal X is bonded by a method based on JIS K6728 "Testing method for polyvinyl butyral".

The preferred lower limit of the amount of acetal groups of the polyvinyl acetal X is 60 mol%, and the preferred upper limit is 85 mol%. By setting the amount of acetal groups of the above-mentioned polyvinyl acetal X to 60 mol% or more, the hydrophobicity of the sound insulation layer can be improved, and the amount of plasticizer required for the sound insulation can be contained to prevent plasticizer Exudation or bleaching. By setting the amount of acetal groups of the polyvinyl acetal X to be 85 mol% or less, the synthesis of polyvinyl acetal X can be facilitated and productivity can be ensured. The lower limit of the amount of acetal groups of the polyvinyl acetal X is more preferably 65 mol%, and still more preferably 68 mol% or more.

The amount of the acetal group can be determined by measuring the amount of ethylene groups to which the acetal group of the polyvinyl acetal X is bonded by a method based on JIS K6728 "Test Method for Polyvinyl Butyraldehyde".

The preferred lower limit of the acetyl group content of the polyvinyl acetal X is 0.1 mol%, and the preferred upper limit is 30 mol%. By setting the amount of the acetyl group of the polyvinyl acetal X to be 0.1 mol% or more, the plasticizer can be contained in an amount necessary for the sound insulation, and bleeding can be prevented. In addition, by setting the amount of acetyl groups of the polyvinyl acetal X to 30 mol% or less, the hydrophobicity of the sound insulation layer can be improved and whitening can be prevented. A more preferable lower limit of the above-mentioned acetyl content is 1 mol%, and a more preferable lower limit is 5 mol%, a particularly preferable lower limit is 8 mol%, and a more preferable upper limit is 25 mol%, and a more preferable upper limit is 20 mol%. The above-mentioned amount of acetyl group is the value obtained by subtracting the total amount of ethylene group bound by the main chain of the ethylene group bound by the acetal group and the amount of ethylene group bound by the hydroxyl group and divided by the ethylene group amount of the main chain The molar fraction calculated from the total amount is expressed as a percentage (mol%).

In particular, in terms of allowing the sound-insulating layer to easily contain a plasticizer in an amount required for the sound insulation, the polyvinyl acetal X is preferably polyethylene with the acetyl group content of 8 mol% or more. Acetal or polyvinyl acetal with an acetal group content of less than 8 mol% and an acetal group content of 65 mol% or more. Furthermore, the polyvinyl acetal X is more preferably polyvinyl acetal in which the amount of acetyl groups is 8 mol% or more, or the amount of acetyl groups is less than 8 mol% and the amount of acetal groups is 68 mol%. The above polyvinyl acetal.

The lower limit of the content of the plasticizer in the sound insulation layer relative to 100 parts by mass of the polyvinyl acetal X is preferably 45 parts by mass, and the upper limit is preferably 100 parts by mass. By setting the content of the above-mentioned plasticizer to 45 parts by mass or more, high sound insulation properties can be exerted, and by setting it to 100 parts by mass or less, it is possible to prevent the bleed-out of the plasticizer and cause the interlayer film for laminated glass When the transparency or adhesion is reduced. The lower limit of the content of the plasticizer is more preferably 50 parts by mass, and the lower limit is more preferably 55 parts by mass, and the upper limit is more preferably 80 parts by mass, the upper limit is still more preferably 75 parts by mass, and the upper limit is more preferably 70 parts by mass. .

Furthermore, the content of the plasticizer in the sound insulation layer can be the content of the plasticizer before the production of the laminated glass, or the content of the plasticizer after the production of the laminated glass.

The content of the plasticizer after the above-mentioned laminated glass can be measured according to the following procedure. That is, first, after the laminated glass is produced, it is allowed to stand for 4 weeks in an environment with a temperature of 25° C. and a humidity of 30%. Thereafter, the laminated glass was cooled with liquid nitrogen, thereby peeling the glass and the interlayer film for laminated glass. Cut the obtained interlayer film for laminated glass in the thickness direction. After standing for 2 hours in an environment with a temperature of 25°C and a humidity of 30%, put a finger or a machine between the protective layer and the sound insulation layer at a temperature of 25°C , Peel off in an environment with a humidity of 30% to obtain a 10g rectangular measurement sample for the sound insulation layer. Use the Soxhlet extractor to extract the plasticizer with diethyl ether for the obtained test sample for 12 hours After that, the plasticizer in the test sample is quantified, and the content of the plasticizer in the sound insulation layer is calculated.

The preferable lower limit of the thickness of the above-mentioned sound insulation layer is 50 μm. By setting the thickness of the above-mentioned sound insulation layer to 50 μm or more, sufficient sound insulation can be exhibited. The lower limit of the thickness of the above-mentioned sound insulation layer is more preferably 80 μm. Furthermore, the upper limit is not particularly limited, and when considering the thickness of the interlayer film for laminated glass, the preferred upper limit is 300 μm.

The above-mentioned protective layer has the function of "preventing a large amount of plasticizer contained in the sound-insulating layer from oozing out and lowering the adhesion between the interlayer film for laminated glass and the glass", and has the function of imparting penetration resistance to the interlayer film for laminated glass effect.

The above-mentioned protective layer preferably contains, for example, polyvinyl acetal Y and a plasticizer, and more preferably contains polyvinyl acetal Y and a plasticizer having a hydroxyl group greater than polyvinyl acetal X.

The above-mentioned polyvinyl acetal Y can be prepared by acetalizing polyvinyl alcohol with aldehyde. The above-mentioned polyvinyl alcohol is usually obtained by saponifying polyvinyl acetate.

In addition, the lower limit of the average degree of polymerization of the polyvinyl alcohol is preferably 200, and the upper limit is 5,000. By setting the average degree of polymerization of the polyvinyl alcohol to 200 or more, the penetration resistance of the interlayer film for laminated glass can be improved, and by setting it to 5,000 or less, the formability of the protective layer can be ensured. The lower limit of the average degree of polymerization of the polyvinyl alcohol is more preferably 500, and the upper limit is more preferably 4,000.

The preferable lower limit of the carbon number of the aldehyde used to acetalize the above polyvinyl alcohol is 3, and the preferable upper limit is 4. By setting the carbon number of the aldehyde to 3 or more, the penetration resistance of the interlayer film for laminated glass becomes higher. By setting the carbon number of the aldehyde to 4 or less, the productivity of polyvinyl acetal Y is improved.

The aldehyde having 3 to 4 carbon atoms may be linear or branched. For example, n-butyraldehyde may be mentioned.

The preferred upper limit of the hydroxyl content of the polyvinyl acetal Y is 33 mol%, which is more The lower limit is 28 mol%. By setting the amount of hydroxyl groups of the polyvinyl acetal Y to 33 mol% or less, the whitening of the interlayer film for laminated glass can be prevented. By setting the amount of hydroxyl groups of the polyvinyl acetal Y to 28 mol% or more, the penetration resistance of the interlayer film for laminated glass becomes higher.

Regarding the above-mentioned polyvinyl acetal Y, a preferable lower limit of the amount of acetal groups is 60 mol%, and a preferable upper limit is 80 mol%. By setting the amount of the acetal group to 60 mol% or more, the plasticizer can be contained in an amount required to exhibit sufficient penetration resistance. By setting the amount of the acetal group to 80 mol% or less, the adhesion between the protective layer and the glass can be ensured. A more preferable lower limit of the amount of acetal groups is 65 mol%, and a more preferable upper limit is 69 mol%.

The preferred upper limit of the amount of acetyl groups of the polyvinyl acetal Y is 7 mol%. By setting the acetyl group content of the polyvinyl acetal Y to 7 mol% or less, the hydrophobicity of the protective layer can be improved and whitening can be prevented. A more preferable upper limit of the amount of acetyl group is 2 mol%, and a more preferable lower limit is 0.1 mol%. In addition, the amount of hydroxyl groups, the amount of acetal groups, and the amount of acetyl groups of polyvinyl acetal A, B, and Y can be measured by the same method as that of polyvinyl acetal X.

The lower limit of the content of the plasticizer in the protective layer relative to 100 parts by mass of the polyvinyl acetal Y is preferably 20 parts by mass, and the upper limit is preferably 45 parts by mass. By setting the above-mentioned plasticizer content to 20 parts by mass or more, penetration resistance can be ensured, and by setting it to 45 parts by mass or less, it can prevent the oozing of the plasticizer and prevent the transparency or transparency of the interlayer film for laminated glass. Then the sex decreases. The lower limit of the content of the plasticizer is more preferably 30 parts by mass, still more preferably the lower limit is 35 parts by mass, the upper limit is more preferably 43 parts by mass, and the upper limit is still more preferably 41 parts by mass. In terms of further improving the sound insulation of the laminated glass, the content of the plasticizer in the protective layer is preferably less than the content of the plasticizer in the sound insulation layer.

Furthermore, the content of the plasticizer in the protective layer can be the same as the plasticizer content before the laminated glass is made. The amount can also be the plasticizer content after the laminated glass is made. The content of the plasticizer after the laminated glass is produced can be measured in the same procedure as the above-mentioned sound insulation layer.

In terms of further improving the sound insulation of laminated glass, the amount of hydroxyl groups of polyvinyl acetal Y is preferably greater than that of polyvinyl acetal X, more preferably 1 mol% or more, and more preferably greater 5 mol% or more, and more preferably 8 mol% or more. By adjusting the amount of hydroxyl groups of polyvinyl acetal X and polyvinyl acetal Y, the content of the plasticizer in the sound insulation layer and the protective layer can be controlled, and the glass transition temperature of the sound insulation layer becomes lower. As a result, the sound insulation of laminated glass is further improved.

Moreover, in terms of further improving the sound insulation of the laminated glass, the content of the plasticizer in the sound insulation layer relative to 100 parts by mass of polyvinyl acetal X (hereinafter also referred to as content X) is preferably more than the above protection The content of the plasticizer in the layer relative to 100 parts by mass of polyvinyl acetal Y (hereinafter also referred to as content Y) is more preferably 5 parts by mass or more, more preferably 15 parts by mass or more, and particularly preferably 20 parts by mass. Parts by mass or more. By adjusting the content X and the content Y, the glass transition temperature of the sound insulation layer becomes lower. As a result, the sound insulation of laminated glass is further improved.

The thickness of the said protective layer should just be adjusted to the range which can exhibit the function of the said protective layer, and is not specifically limited. Among them, when the protective layer has unevenness, it is preferable to thicken it as much as possible in a manner that can suppress the transfer of the unevenness pair to the interface of the sound insulation layer directly connected. Specifically, the lower limit of the thickness of the protective layer is preferably 100 μm, more preferably 300 μm, furthermore preferably 400 μm, and particularly preferably 450 μm. The upper limit of the thickness of the protective layer is not particularly limited. In order to ensure the thickness of the sound insulation layer to the extent that sufficient sound insulation can be achieved, the upper limit is substantially about 500 μm.

As a method of manufacturing the above-mentioned sound insulation interlayer film, there is no particular limitation, for example, Examples include a method in which the sound-insulating layer and the protective layer are formed into a sheet by a usual film forming method such as an extrusion method, a calendering method, and a pressing method.

The manufacturing method of the interlayer film for laminated glass of the present invention is not particularly limited, and a previously known manufacturing method can be used.

In the present invention, as a method of forming a plurality of recesses on at least one surface of the interlayer film for laminated glass, for example, an embossing roll method, a calender roll method, a profile extrusion method, and a lip die using melt fracture Extrusion embossing method, etc. Among them, the embossing roll method is preferred in terms of easily obtaining a shape in which the adjacent bottom continuous groove-shaped concave portions are regularly arranged.

As the embossing roll used in the embossing roll method, for example, the following embossing rolls are used. The embossing rolls use abrasive materials such as alumina or silica to perform sandblasting on the surface of the metal roll to reduce excessive surface area. The peaks are polished by vertical polishing or the like to have an embossed pattern (concave-convex pattern) on the roller surface. In addition to this, an embossing roll having an embossing pattern (concave and convex pattern) on the surface of the roll by transferring the embossed pattern (concave-convex pattern) to the surface of a metal roll using an engraving mill can also be mentioned. Furthermore, the embossing roll etc. which have an embossing pattern (concave-convex pattern) on the roll surface by etching (etching) are mentioned.

In addition, the laminated glass in which the intermediate film for laminated glass of the present invention is laminated between a pair of glass plates is also one of the present invention.

The above-mentioned glass plate can use commonly used transparent plate glass. For example, inorganic glass such as float plate glass, polished plate glass, patterned glass, laminated glass, wire plate glass, colored plate glass, heat-absorbing glass, heat reflective glass, and green glass can be cited. In addition, it can also be used as an anti-ultraviolet glass with an ultraviolet shielding coating formed on the surface of the glass. Furthermore, organic plastic plates, such as polyethylene terephthalate, polycarbonate, and polyacrylate, can also be used.

As the above-mentioned glass plate, two or more types of glass plates can be used. For example, a laminated glass formed by laminating the interlayer film for laminated glass of the present invention between a transparent float flat glass and a colored glass plate such as green glass. In addition, as the above-mentioned glass plate, two or more glass plates with different thicknesses may be used.

The laminated glass of the present invention can be preferably manufactured by a vacuum degassing method.

In the vacuum degassing method, the laminated body with the interlayer film for laminated glass laminated between at least two glass plates is put into a rubber bag for reduced pressure suction, while leaving the residue between the glass plate and the interlayer film The air is removed while pre-compression bonding is performed, and then, for example, it is heated and pressurized in an autoclave to perform full-compression bonding. Here, by simultaneously performing degassing and heating during the pre-compression bonding, the manufacturing time can be greatly shortened and the production efficiency can be improved. By using the interlayer film for laminated glass of the present invention, even if degassing and heating are performed at the same time during pre-compression bonding, it is possible to prevent pre-sealing from being caused, and to obtain a layer with high degassing properties and high transparency. He glass.

According to the present invention, it is possible to provide an interlayer film for laminated glass that can be produced in a vacuum degassing method that can exhibit high degassing and high transparency of laminated glass, and an interlayer film using the laminated glass Laminated glass.

1‧‧‧Choose any recess

2‧‧‧The recess adjacent to any selected recess

3‧‧‧The recess adjacent to any selected recess

A‧‧‧The distance between recess 1 and recess 2

B‧‧‧The distance between recess 1 and recess 3

20‧‧‧The surface of the interlayer film for laminated glass

21‧‧‧Continuous groove-shaped recess at the bottom

22‧‧‧Protrusion

30‧‧‧The surface of the interlayer film for laminated glass

31‧‧‧Continuous groove-shaped recess at the bottom

32‧‧‧Protrusion

33‧‧‧The line connecting the shortest distance between the bottoms of the continuous groove-shaped recesses of adjacent bottoms

34‧‧‧The line drawn at the center of the line that connects the shortest distance between the bottoms of the adjacent bottom continuous groove-shaped recesses is perpendicular to the line of the shortest distance between the bottoms of the connection

Fig. 1 is a schematic diagram showing an example of an interlayer film for laminated glass in which groove-shaped recesses with continuous bottoms are equally spaced, and adjacent recesses are arranged in parallel on the surface.

Fig. 2 is a schematic diagram showing an example of an interlayer film for laminated glass in which groove-shaped recesses with continuous bottoms are equally spaced, and adjacent recesses are arranged in parallel on the surface.

Fig. 3 is a schematic diagram showing an example of an interlayer film for laminated glass in which the recesses of the bottom continuous groove are not equally spaced, but the adjacent recesses are arranged in parallel on the surface.

Fig. 4 is a schematic diagram for explaining the radius of rotation R of the bottom of the concave portion with a continuous groove at the bottom and the interval Sm of the concave portion.

Figure 5 is the direction along the line connecting the shortest distance between the bottom of the continuous groove-shaped recesses of adjacent bottoms. When the roughness curve is drawn according to JIS B 0601 (1994), the point where the height reaches the maximum is not located at the bottom of the connection. A schematic diagram of the interlayer film for laminated glass at the center of the line of the shortest distance between the bottoms.

Hereinafter, examples are given to further describe the aspects of the present invention in detail, but the present invention is not limited to these examples.

(Example 1)

(1) Preparation of resin composition

Compared with polyvinyl butyraldehyde obtained by acetalizing polyvinyl alcohol with an average degree of polymerization of 1700 with n-butyraldehyde (acetyl group content 1 mol%, butyraldehyde group content 69 mol%, hydroxyl group content 30 mol% Ear%) 100 parts by mass, 40 parts by mass of triethylene glycol bis(2-ethylhexanoate) (3GO) was added as a plasticizer, and kneaded sufficiently with a mixing roller to obtain a resin composition.

(2) Production of interlayer film for laminated glass

By extruding the obtained resin composition, an interlayer film for laminated glass with a thickness of 760 μm was obtained.

(3) Concave and convex

As the first step, random uneven shapes are transferred to both surfaces of the interlayer film for laminated glass by the following procedure. First, use a sandblasting agent to apply random irregularities on the surface of the iron roller, then vertically grind the iron roller, and then use a finer sandblasting agent to apply fine unevenness to the polished flat part, thereby obtaining a coarse main embossing A pair of rollers with the same shape as the micro embossing. Using the pair of rollers as a concavo-convex shape transfer device, random concavo-convex shapes were transferred to both sides of the obtained interlayer film for laminated glass. As the transfer conditions at this time, the temperature of the interlayer film for laminated glass was set to 80°C, the temperature of the above-mentioned roller was set to 145°C, the line speed was set to 10m/min, and the line width was set to 1.5m. The pressing pressure is set to 0~200kN/m.

As the second step, the surface of the interlayer film for laminated glass is provided with groove-shaped (line-shaped) concavities and convexities with a continuous bottom in the following procedure. A pair of rollers consisting of a metal roller whose surface is polished using a triangular oblique line mill and a rubber roller with a JIS hardness of 45 to 75 is used as the uneven shape transfer device. The regular concave-convex shape interlayer film for laminated glass is passed through the concave-convex shape transfer device, and the first surface of the interlayer film for laminated glass is formed parallel and equally spaced as the bottom continuous groove-shaped (line-shaped) recesses The bumps. As the transfer conditions at this time, the temperature of the interlayer film for laminated glass was normal temperature, the roller temperature was 140° C., the linear velocity was 10 m/min, and the pressing pressure was 500 kPa.

Then, the same operation is performed on the second surface of the interlayer film for laminated glass, and a continuous groove-shaped (line-shaped) concave portion is provided at the bottom.

(4) Measurement of unevenness on the first surface and the second surface

By a method based on JIS B 0601 (1994), the interval Sm and the roughness Rz of the groove-shaped recesses at the bottom of the first surface and the second surface of the obtained interlayer film for laminated glass were measured. Furthermore, the measuring direction is set as the direction perpendicular to the continuous groove at the bottom, at the critical value =2.5mm, reference length=2.5mm, evaluation length=12.5mm, tip radius=2μm, tip angle=60°, measurement speed=0.5mm/s. Since there is unevenness in the shape of the surface of the interlayer film for laminated glass, 5 points were measured in the plane, and the average value was used as the evaluation result.

In addition, use a single-edged razor (manufactured by FEATHER Safety Razor, FAS-10) along the direction perpendicular to the direction of the continuous groove at the bottom and parallel to the film thickness direction to avoid deformation of the cut surface. Press down in the direction parallel to the thickness direction without sliding in the direction perpendicular to the recess to cut the interlayer film for laminated glass, and observe its cross section with a microscope ("DSX-100" manufactured by Olympus). Shooting at a measuring magnification of 277 times, and then using the measurement software in the accompanying software to obtain the bottom incission of the groove that is drawn and continuous with the bottom under the condition that the captured image is enlarged and displayed at 50μm/20mm The radius of the circle when it is round (ie the radius of rotation R). In addition, the environment at the time of measurement was set to 23°C and 30RH%.

(5) Manufacturing of laminated body

The obtained interlayer film for laminated glass was sandwiched between two transparent glass plates (length 30 cm × width 30 cm × thickness 2.5 mm), and the protruding part was cut to obtain a laminate. Preheat the obtained laminate in an oven until the surface temperature of the glass becomes 50°C, then transfer it to a rubber bag, connect the rubber bag to a suction decompressor, heat it and keep it under a reduced pressure of -600mmHg After 10 minutes, the laminate was heated so that the temperature (pre-compression temperature) of the laminate became 90°C, and then returned to atmospheric pressure to complete the pre-compression.

(Examples 2 to 5, Comparative Examples 1 to 6)

Change the amount of acetyl group, the amount of butyraldehyde group and the amount of hydroxyl, and the content of plasticizer of the polyvinyl butyral used in the manner shown in Table 1, and change the use of a triangular diagonal mill to polish the surface The shape of the processed metal roll is such that the radius of rotation R, the interval Sm, and the roughness Rz of the groove-shaped recesses that are continuous at the bottom of the first surface and the second surface are as shown in Table 1. In addition, by The interlayer film and laminate for laminated glass were produced in the same manner as in Example 1.

(Example 6)

(1) Preparation of resin composition

Compared with polyvinyl butyraldehyde obtained by acetalizing polyvinyl alcohol with an average degree of polymerization of 1700 with n-butyraldehyde (acetyl group content 1 mol%, butyraldehyde group content 69 mol%, hydroxyl group content 30 mol% Ear%) 100 parts by mass, and 40 parts by mass of triethylene glycol bis(2-ethylhexanoate) (3GO) as a plasticizer, as an adhesive modifier, and added in the middle of the obtained laminated glass The magnesium content in the film is a 1:1 mixture with a mass ratio of magnesium 2-ethylbutyrate and magnesium acetate in an amount of 50 ppm, which is sufficiently kneaded with a mixing roller to obtain a resin composition.

(2) Production of interlayer film for laminated glass

By extruding the obtained resin composition, an interlayer film for laminated glass with a thickness of 760 μm was obtained.

(3) Concave and convex

As the first step, random uneven shapes are transferred to both surfaces of the interlayer film for laminated glass by the following procedure. First, use a sandblasting agent to apply random irregularities on the surface of the iron roller, then vertically grind the iron roller, and then use a finer sandblasting agent to apply fine unevenness to the polished flat part, thereby obtaining a coarse main embossing A pair of rollers with the same shape as the micro embossing. Using the pair of rollers as a concavo-convex shape transfer device, random concavo-convex shapes were transferred to both sides of the obtained interlayer film for laminated glass. As the transfer conditions at this time, the temperature of the interlayer film for laminated glass was set to 80°C, the temperature of the above-mentioned roller was set to 145°C, the line speed was set to 10m/min, and the line width Set to 1.5m, and set the pressing pressure to 0~200kN/m.

As the second step, the surface of the interlayer film for laminated glass is provided with groove-shaped (line-shaped) concavities and convexities with a continuous bottom in the following procedure. A pair of rollers consisting of a metal roller whose surface is polished using a triangular oblique line mill and a rubber roller with a JIS hardness of 45 to 75 is used as the uneven shape transfer device. The regular concave-convex shape interlayer film for laminated glass is passed through the concave-convex shape transfer device, and the first surface of the interlayer film for laminated glass is formed parallel and equally spaced as the bottom continuous groove-shaped (line-shaped) recesses The bumps. As the transfer conditions at this time, the temperature of the interlayer film for laminated glass is set to 80°C, the roller temperature is set to 140°C, the line speed is set to 10m/min, the line width is set to 1.5m, and the pressing Set to 0~500kPa.

Then, the same operation is performed on the second surface of the interlayer film for laminated glass, and a continuous groove-shaped (line-shaped) concave portion is provided at the bottom. In addition, the intersection angle θ between the groove-shaped concave portion having the continuous bottom of the first surface and the groove-shaped concave portion having the continuous bottom of the second surface is 90°.

(4) Measurement of unevenness on the first surface and the second surface

By a method based on JIS B 0601 (1994), the interval Sm and the roughness Rz of the groove-shaped recesses at the bottom of the first surface and the second surface of the obtained interlayer film for laminated glass were measured. Furthermore, the measurement direction is set as the direction perpendicular to the continuous groove shape at the bottom, at critical value=2.5mm, reference length=2.5mm, evaluation length=12.5mm, tip radius of stylus=2μm, tip angle=60° , Measure under the condition of measuring speed=0.5mm/s. Since there is unevenness in the shape of the surface of the interlayer film for laminated glass, 5 points were measured in the plane, and the average value was used as the evaluation result.

In addition, a single-edged razor (manufactured by FEATHER Safety Razor, FAS-10) is used, along with The direction of the continuous groove at the bottom is perpendicular and parallel to the film thickness direction to avoid deformation of the cut surface. The razor is in a direction parallel to the thickness direction without sliding in the direction perpendicular to the recess Press to cut the interlayer film for laminated glass, observe the cross-section with a microscope ("DSX-100" manufactured by Olympus), take a picture with a measuring magnification of 277 times, and then magnify it to 50μm/20mm When the image is taken, use the measurement software in the accompanying software to obtain the radius of the circle (ie, the radius of rotation R) when the circle inscribed at the bottom of the groove continuous to the bottom is drawn. In addition, the environment at the time of measurement was set to 23°C and 30RH%.

In addition, along the direction of the line connecting the shortest distance between the bottoms of the adjacent bottom continuous groove-shaped recesses of the obtained interlayer film for laminated glass, the roughness curve was drawn in accordance with JIS B 0601 (1994), and the result was obtained The point where the height of the roughness curve reaches the maximum is located at the center of the line of the shortest distance between the bottom of the connection. That is, the adjacent bottom continuous groove-shaped recesses of the obtained interlayer for laminated glass have a symmetrical shape when the axis is perpendicular to the line connecting the shortest distance between the bottommost parts.

(5) Manufacturing of laminated body

The obtained interlayer film for laminated glass was sandwiched between two transparent glass plates (length 30 cm × width 30 cm × thickness 2.5 mm), and the protruding part was cut to obtain a laminate. Preheat the obtained laminate in an oven until the surface temperature of the glass becomes 50°C, then transfer it to a rubber bag, connect the rubber bag to a suction decompressor, heat it and keep it under a reduced pressure of -600mmHg After 10 minutes, the laminate was heated so that the temperature (pre-compression temperature) of the laminate became 90°C, and then returned to atmospheric pressure to complete the pre-compression.

(Examples 7~14)

Change the amount of acetyl group, butyraldehyde group and the amount of polyvinyl butyraldehyde used in the manner shown in Table 2. The amount of hydroxyl group, the content of plasticizer, the content of magnesium (Mg), and the shape of the metal roller whose surface is grinded with a triangular diagonal mill is changed to make the bottom of the first surface and the second surface continuous The rotation radius R, the interval Sm, the roughness Rz, and the intersection angle θ of the groove-shaped recesses were as shown in Table 2. Except for this, the interlayer film and laminate for laminated glass were produced by the same method as in Example 6. .

In addition, along the direction of the line connecting the shortest distance between the bottoms of the adjacent bottom continuous groove-shaped recesses of the interlayer films for laminated glass of Examples 7 to 11, a roughness curve was drawn in accordance with JIS B 0601 (1994), As a result, the point where the height of the obtained roughness curve reaches the maximum is located at the center of the line of the shortest distance between the bottom of the connection. That is, the adjacent bottom continuous groove-shaped recesses of the interlayer films for laminated glass obtained in Examples 7 to 11 have a symmetrical shape when the line perpendicular to the line connecting the shortest distance between the bottoms is the axis.

On the other hand, along the direction of the line connecting the shortest distance between the bottoms of the adjacent bottom continuous groove-shaped recesses of the interlayer films for laminated glass of Examples 12-14, the roughness is drawn according to JIS B 0601 (1994) Curve, the point where the height of the obtained roughness curve reaches the maximum is not at the center of the line of the shortest distance between the bottom of the connection. That is, the adjacent bottom continuous groove-shaped recesses of the interlayer film for laminated glass obtained in Examples 12 to 14 are not symmetrical when the line perpendicular to the line connecting the shortest distance between the bottoms is the axis.

(Example 15)

(Preparation of resin composition for protective layer)

Compared with polyvinyl butyraldehyde obtained by acetalizing polyvinyl alcohol with an average degree of polymerization of 1700 with n-butyraldehyde (acetyl group content 1 mol%, butyraldehyde group content 69 mol%, hydroxyl group content 30 mol% Ear%) 100 parts by mass, add triethylene glycol bis(2-ethylhexanoate) (3GO) as a plasticizer 36 parts by mass. Furthermore, as an adhesive strength regulator, a mixture of magnesium 2-ethylbutyrate and magnesium acetate (1:1 by mass ratio) was added so that the content of magnesium became 50 ppm. Kneading was sufficiently performed with a mixing roller to obtain a resin composition for a protective layer.

(Preparation of resin composition for sound insulation layer)

Compared to polyvinyl butyral obtained by acetalizing polyvinyl alcohol with an average degree of polymerization of 2300 with n-butyraldehyde (12.5 mole% of acetyl groups, 64 mole% of butyraldehyde groups, and 23.5 mole% of hydroxyl groups). Ear %) 100 parts by mass, 76.5 parts by mass of triethylene glycol bis(2-ethylhexanoate) (3GO) as a plasticizer was added, and the mixture was sufficiently kneaded with a mixing roller to obtain a resin composition for a sound insulation layer.

(Production of interlayer film for laminated glass)

By co-extruding the resin composition for the sound insulation layer and the resin composition for the protection layer, a first protective layer (thickness 300 μm), sound insulation layer (thickness 100 μm), and second The protective layer (thickness 400μm) is an intermediate film for laminated glass with a three-layer structure.

(Giving of bumps)

As the first step, random uneven shapes are transferred to both surfaces of the interlayer film for laminated glass by the following procedure. First, use a sandblasting agent to apply random irregularities on the surface of the iron roller, then vertically grind the iron roller, and then use a finer sandblasting agent to apply fine unevenness to the polished flat part, thereby obtaining a coarse main embossing A pair of rollers with the same shape as the micro embossing. Using the pair of rollers as a concavo-convex shape transfer device, random concavo-convex shapes were transferred to both sides of the obtained interlayer film for laminated glass. As the transfer conditions at this time, the temperature of the interlayer film for laminated glass was set to 80°C, the temperature of the above-mentioned roller was set to 145°C, the line speed was set to 10m/min, and the line width was set to 1.5m. The pressing pressure is set to 0~200kN/m.

As the second step, apply the following procedure to the surface of the interlayer film for laminated glass Give the bottom continuous groove-shaped (line-shaped) unevenness. A pair of rollers consisting of a metal roller whose surface is polished using a triangular oblique line mill and a rubber roller with a JIS hardness of 45 to 75 is used as the uneven shape transfer device. The regular concave-convex shape interlayer film for laminated glass is passed through the concave-convex shape transfer device, and the first surface of the interlayer film for laminated glass is formed parallel and equally spaced as the bottom continuous groove-shaped (line-shaped) recesses The bumps. As the transfer conditions at this time, the temperature of the interlayer film for laminated glass is set to 80°C, the roller temperature is set to 140°C, the line speed is set to 10m/min, the line width is set to 1.5m, and the pressing Set to 0~500kPa.

Then, the same operation is performed on the second surface of the interlayer film for laminated glass, and a continuous groove-shaped (line-shaped) concave portion is provided at the bottom. In addition, the intersection angle θ between the groove-shaped concave portion having a continuous bottom on the first surface and the groove-shaped concave portion having a continuous bottom on the second surface was set to 20°.

By the same method as in Example 1, the radius of rotation R, the interval Sm, and the roughness Rz of the continuous groove-shaped recesses on the bottom of the first surface and the second surface were measured. In addition, along the direction of the line connecting the shortest distance between the bottoms of the adjacent bottom continuous groove-shaped recesses of the obtained interlayer film for laminated glass, the roughness curve was drawn in accordance with JIS B 0601 (1994), and the result was obtained The point where the height of the roughness curve reaches the maximum is located at the center of the line of the shortest distance between the bottom of the connection. That is, the adjacent bottom continuous groove-shaped recesses of the obtained interlayer for laminated glass have a symmetrical shape when the axis is perpendicular to the line connecting the shortest distance between the bottommost parts.

(Manufacturing of laminated body and laminated glass)

The obtained interlayer film for laminated glass was sandwiched between two transparent glass plates (length 30 cm × width 30 cm × thickness 2.5 mm), and the protruding part was cut to obtain a laminate. The obtained laminate is preheated in an oven until the surface temperature of the glass becomes 50°C, then transferred to a rubber bag, and the rubber The bag is connected to a suction decompressor, and the bag is heated while keeping it under a reduced pressure of -600mmHg for 10 minutes, and heated so that the temperature of the laminate (pre-compression temperature) becomes 90°C, then return to atmospheric pressure. Pre-crimping.

Put the pre-compressed laminate into an autoclave and keep it for 10 minutes at a temperature of 140°C and a pressure of 1300kPa, then lower the temperature to 50°C and return to atmospheric pressure, thereby ending the formal pressing and obtaining a layer He glass.

(Determination of the content of plasticizer)

After making the laminated glass, let it stand for 4 weeks at a temperature of 25°C and a humidity of 30%. Thereafter, the laminated glass was cooled with liquid nitrogen, thereby peeling the glass and the interlayer film for laminated glass. Cut the obtained interlayer film for laminated glass in the thickness direction. After standing for 2 hours in an environment with a temperature of 25°C and a humidity of 30%, put a finger or a machine between the protective layer and the sound insulation layer at a temperature of 25°C , Peel off in an environment with a humidity of 30% to obtain 10g rectangular measurement samples for the protective layer and sound insulation layer. For the obtained measurement sample, use the Soxhlet extractor to extract the plasticizer with diethyl ether for 12 hours, and then quantify the plasticizer in the measurement sample to obtain the content of the plasticizer in the protective layer and the intermediate layer .

(Examples 16-21, Comparative Examples 7-10)

Change the amount of acetyl group, butyraldehyde group and hydroxyl group, plasticizer content, magnesium (Mg) content, the thickness of the first protective layer, and the second protective layer of the polyvinyl butyral used in the manner shown in Table 3. The thickness of the layer is changed, and the shape of the metal roller whose surface is ground with a triangular diagonal mill is changed to make the radius of rotation R, the interval Sm, and the interval Sm of the continuous groove-shaped recesses on the bottom of the first surface and the second surface The roughness Rz and the crossing angle θ were as shown in Table 3. Except for this, the interlayer film for laminated glass, the laminated body, and the laminated glass were produced by the same method as in Example 15.

In addition, along the direction of the line connecting the shortest distance between the bottoms of the adjacent bottom continuous groove-shaped recesses of the interlayer films for laminated glass of Examples 16-21, a roughness curve was drawn in accordance with JIS B 0601 (1994), As a result, the point where the height of the obtained roughness curve reaches the maximum is located at the center of the line of the shortest distance between the bottom of the connection. That is, the adjacent bottom continuous groove-shaped recesses of the interlayer films for laminated glass obtained in Examples 16 to 21 have a symmetrical shape with the line perpendicular to the line connecting the shortest distance between the bottoms as the axis.

(Evaluation)

Regarding the interlayer film for laminated glass and the laminated glass obtained in the Examples and Comparative Examples, the parallel light transmittance of the laminated body after the pre-compression bonding was evaluated by the following method.

That is, in accordance with JIS K 7105, a haze meter (manufactured by Murakami Color Laboratory Co., Ltd., HM-150) was used to measure the parallel light transmittance Tp (%) of the laminated body after the pre-compression bonding when the laminated glass was manufactured.

The measurement position is the central part where the two diagonal lines of the laminate intersect, and a total of 5 points are located 10 cm from each vertex of the laminate in the diagonal direction, and the average value is taken as Tp.

Before the measurement, the laminate was cut out of 5 cm×5 cm with the above measurement point as the center to prepare a sample for measurement.

Furthermore, the decrease in the transparency of the laminated glass is due to poor outgassing during pre-compression bonding. Therefore, compared to evaluating the foamability of laminated glass, the degassing property of the interlayer film for laminated glass can be evaluated more precisely by measuring the parallel light transmittance of the laminated body after pre-compression bonding.

The results are shown in Table 1, Table 2, and Table 3.

In addition, it is changed so that the intersection angle θ between the groove-shaped concave portion with a continuous bottom on the first surface and the groove-shaped concave portion with a continuous bottom on the second surface becomes 20°. Example 1~5 and Comparative Examples 1~6 are the same methods used to make interlayer film and laminate for laminated glass The results showed the same degassing properties as in Examples 1 to 5 and Comparative Examples 1 to 6.

[Industrial availability]

According to the present invention, it is possible to provide an interlayer film for laminated glass that can be produced in a vacuum degassing method that can exhibit high degassing and high transparency laminated glass, and a layer using the interlayer film for laminated glass He glass.

Claims (10)

An interlayer film for laminated glass, which has a plurality of recesses on at least one surface, and the recesses have a groove shape with a continuous bottom, and the adjacent recesses of the continuous groove shape at the bottom are arranged regularly, and are characterized in that the bottom is continuous The radius of rotation R of the bottom of the groove-shaped recess is 45μm or less, and the roughness is drawn in the direction of the line connecting the shortest distance between the bottom of the adjacent bottom continuous groove-shaped recesses according to JIS B 0601 (1994) In the case of a curve, the point at which the height reaches the maximum is not located at the center of the line of the shortest distance between the bottoms of the above connections. For example, the interlayer film for laminated glass in the first item of the scope of patent application, wherein the radius of rotation R of the bottom of the concave portion with a continuous groove at the bottom is 15μm or less. For example, the interlayer film for laminated glass of item 1 or 2 of the scope of patent application, wherein the rotation radius R of the bottom of the continuous groove-shaped concave portion is 0.1 μm or more. For example, the first or second interlayer film for laminated glass in the scope of the patent application, wherein the interval Sm between the continuous groove-shaped recesses at the bottom is 400 μm or less. For example, the first or second interlayer film for laminated glass in the scope of patent application, wherein the roughness Rz of the concave portion of the continuous groove at the bottom is 60μm or less. For example, the interlayer film for laminated glass of the first or second patent application, wherein the surface with a plurality of concave portions further has a plurality of convex portions, and the top of the convex portion is not flat. For example, the interlayer film for laminated glass of item 1 or 2 of the scope of patent application, which contains at least one metal selected from the group consisting of alkali metals, alkaline earth metals and magnesium, and the above is selected from alkali metals, alkaline earth metals and magnesium The content of at least one metal in the group is 1 ppm or more and 500 ppm or less. For example, the first or second interlayer film for laminated glass in the scope of the patent application has a plurality of recesses on one surface and the surface opposite to the one surface. The recesses have a groove shape with a continuous bottom, and the one surface The intersection angle θ of the groove-shaped concave portion with the continuous bottom and the concave portion with the groove-shaped bottom continuous on the surface on the opposite side is more than 0° and 90° or less. For example, the first or second interlayer film for laminated glass in the scope of patent application has a laminated structure having a first resin layer, a second resin layer, and a third resin layer in order along the thickness direction, and the first resin layer is The thickness is different from the thickness of the third resin layer described above. A laminated glass, in which the interlayer film for laminated glass of item 1, 2, 3, 4, 5, 6, 7, 8, or 9 in the scope of patent application is laminated between a pair of glass plates.

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